US2533193A - 2, 3-derivatives of 1, 4-dihaloanthraquinones - Google Patents
2, 3-derivatives of 1, 4-dihaloanthraquinones Download PDFInfo
- Publication number
- US2533193A US2533193A US739250A US73925047A US2533193A US 2533193 A US2533193 A US 2533193A US 739250 A US739250 A US 739250A US 73925047 A US73925047 A US 73925047A US 2533193 A US2533193 A US 2533193A
- Authority
- US
- United States
- Prior art keywords
- dihalo
- derivatives
- parts
- dimethylanthraquinone
- dihaloanthraquinones
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- GDALETGZDYOOGB-UHFFFAOYSA-N Acridone Natural products C1=C(O)C=C2N(C)C3=CC=CC=C3C(=O)C2=C1O GDALETGZDYOOGB-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- FZEYVTFCMJSGMP-UHFFFAOYSA-N acridone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3NC2=C1 FZEYVTFCMJSGMP-UHFFFAOYSA-N 0.000 description 3
- -1 aromatic thiols Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 3
- QQPQYWGNVMIGAF-UHFFFAOYSA-N 9,10-dioxoanthracene-1,2-dicarboxylic acid Chemical class C1=CC=C2C(=O)C3=C(C(O)=O)C(C(=O)O)=CC=C3C(=O)C2=C1 QQPQYWGNVMIGAF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- GNRPVZNNVOGXHD-UHFFFAOYSA-N 1,2-dimethylanthracene-9,10-dione Chemical class C1=CC=C2C(=O)C3=C(C)C(C)=CC=C3C(=O)C2=C1 GNRPVZNNVOGXHD-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- RBGUKBSLNOTVCD-UHFFFAOYSA-N 1-methylanthracene-9,10-dione Chemical class O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C RBGUKBSLNOTVCD-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- HUKPVYBUJRAUAG-UHFFFAOYSA-N 7-benzo[a]phenalenone Chemical compound C1=CC(C(=O)C=2C3=CC=CC=2)=C2C3=CC=CC2=C1 HUKPVYBUJRAUAG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- NBOMNTLFRHMDEZ-UHFFFAOYSA-N thiosalicylic acid Chemical compound OC(=O)C1=CC=CC=C1S NBOMNTLFRHMDEZ-UHFFFAOYSA-N 0.000 description 1
- 229940103494 thiosalicylic acid Drugs 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
Definitions
- the present invention relates to lA-dihalo- 2.3-dimethyl and dicarboxyanthraquinones and more particularly to the 1.4-dichloro compounds.
- vat dyes are those of the acridone and thioxanthone series. It has been proposed in the past to produce such dyes by the reaction of l-halo-anthraquinones with anthranilic acid or thiosalicylic acid. For the most part dyestuffs of these series have been rather simply constituted primarily for the reason that substituted anthranilic and salicylic acids necessary for the preparation of the more complex dyestuffs are not readily available.
- X is halogen, such as, chlorine or bromine and preferably is chlorine.
- the 1.4 dihalo 2.3 dimethylanthraquinones falling within the above formula are conveniently prepared by reacting 2.3-dimethylanthraquinone with suliuryl chloride in an inert solvent, such as, toluene, nitrobenzene and the like at a temperature of about 80 to 120 C.
- the halogenation of the 2.3-dimethylanthraquinone may be eifected with a mixture of chlorine or bromine in sulfuric acid or chlorsulfonic acid at a temperature ranging from 0 to 50 C.
- the 2.3-dimethylanthraquinone which may be prepared by condensing 2.3-dimethylbutadiene with a-naphthoquinone is described in Vol. 36, page 3171 of Chemical Abstracts.
- 1.4-dihalo-2.3-dicarboxylic anthraquinones are prepared by oxidizing the 1.4-dihalo-2.3-di- 2 methylanthraquinones with nitric acid or a mixture of manganese dioxide and sulfuric acid. It is preferable to effect the reaction in a closed vessel at a temperature ranging from about 180 to 220 C.
- Both the l.4-dihalo-2.3-dimethylanthraquinones and the corresponding 2.3-dicarboxylic acids are capable of undergoing many different chemical reactions leading to valuable intermediates for the preparation of dyes and other dye intermediates. Thus, both can be reduced to the corresponding hydroquinone. They can also be sulfonated, nitrated, halogenated, esterified and aminated with ammonia and aliphatic and aromatic amines. The dicarboxylic acid derivatives may also be amidated with ammonia and the aforementioned amines.
- the 1.4-dihalo- 2.3-dimethylanthraquinones are particularly valuable as intermediates for the preparation of benzanthrone by reaction with glycerol.
- the chief use of the corresponding 2.3-dicarboxy derivatives is as previously stated in the preparation of dyestuffs of the acridone and thioxanthone series.
- Example I 49.2 parts of 2.3-dimethylanthraquinone are added to a solution of '75 parts of sulfuryl chloride and 5 parts of iodine in 150 parts of nitrobenzene. The mixture was heated at to C. for five hours during which time the 1.4-dichloro- 2.3-dimethylanthraquinone precipitated from the hot reaction mixture. Upon cooling the mixture to 10 C. there were obtained 41.5 parts of pure 1.4-dichloro-2.3-dimethylanthraquinone melting at 231 to 234 C.
- Example II 12 parts of the 1.4-dichloro-2.3-dimethylanthraquinone obtained as in Example I and 75 parts of 20% nitric acid are heated to 200 C. in a pressure vessel for six hours. The yellow crystalline solid obtained was dissolved in dilute sodium hydroxide maintained at 60 C., the solution filtered andthe product recovered by acidification with hydrochloric acid, followed by filtration. There were obtained 9 parts of 1.4- dichlorc-2.3-dicarboxyanthraquinone melting at about 320 C.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented Dec. 5, 1950 2.3-DERIVATIVES OF lA-DIHALOANTHRA- QUINONES Fritz Max, Easton, Pa., and David I. Randall, .lhillipsburg, N. 3., assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. 1 Application April 3, 1947, Serial No. 739,250-
2 Claims.
The present invention relates to lA-dihalo- 2.3-dimethyl and dicarboxyanthraquinones and more particularly to the 1.4-dichloro compounds.
A very valuable group of vat dyes are those of the acridone and thioxanthone series. It has been proposed in the past to produce such dyes by the reaction of l-halo-anthraquinones with anthranilic acid or thiosalicylic acid. For the most part dyestuffs of these series have been rather simply constituted primarily for the reason that substituted anthranilic and salicylic acids necessary for the preparation of the more complex dyestuffs are not readily available.
It has now been ascertained that complex dyestuffs of the acridone and thioxanthone series can be readily prepared from 1.4-dihalo-2.3-dicarboxyanthraquinones by reacting the same with substituted aromatic thiols and amines. It has likewise been discovered that the 1.4-dihalo- 2.3-dicarboxyanthraquinones may be very easily prepared by oxidation from 1.4-dihalo-2.3-dimethylanthraquinones. Said l.4-dihalo-2.3dimethyl and dicarboxyanthraquinones and their preparation constitute the purposes and objects of the present invention.
The compounds contemplated by the present invention have the following structural formula wherein both Ys have the same value and are either methyl or carboxy:
H ox
and X is halogen, such as, chlorine or bromine and preferably is chlorine.
The 1.4 dihalo 2.3 dimethylanthraquinones falling within the above formula are conveniently prepared by reacting 2.3-dimethylanthraquinone with suliuryl chloride in an inert solvent, such as, toluene, nitrobenzene and the like at a temperature of about 80 to 120 C. Similarly, the halogenation of the 2.3-dimethylanthraquinone may be eifected with a mixture of chlorine or bromine in sulfuric acid or chlorsulfonic acid at a temperature ranging from 0 to 50 C. The 2.3-dimethylanthraquinone which may be prepared by condensing 2.3-dimethylbutadiene with a-naphthoquinone is described in Vol. 36, page 3171 of Chemical Abstracts.
1.4-dihalo-2.3-dicarboxylic anthraquinones are prepared by oxidizing the 1.4-dihalo-2.3-di- 2 methylanthraquinones with nitric acid or a mixture of manganese dioxide and sulfuric acid. It is preferable to effect the reaction in a closed vessel at a temperature ranging from about 180 to 220 C.
Both the l.4-dihalo-2.3-dimethylanthraquinones and the corresponding 2.3-dicarboxylic acids are capable of undergoing many different chemical reactions leading to valuable intermediates for the preparation of dyes and other dye intermediates. Thus, both can be reduced to the corresponding hydroquinone. They can also be sulfonated, nitrated, halogenated, esterified and aminated with ammonia and aliphatic and aromatic amines. The dicarboxylic acid derivatives may also be amidated with ammonia and the aforementioned amines. The 1.4-dihalo- 2.3-dimethylanthraquinones are particularly valuable as intermediates for the preparation of benzanthrone by reaction with glycerol. On the other hand, the chief use of the corresponding 2.3-dicarboxy derivatives is as previously stated in the preparation of dyestuffs of the acridone and thioxanthone series.
The invention is further explained by the following examples vbut it is to be understood that these examples are illustrative and not limitative:
Example I 49.2 parts of 2.3-dimethylanthraquinone are added to a solution of '75 parts of sulfuryl chloride and 5 parts of iodine in 150 parts of nitrobenzene. The mixture was heated at to C. for five hours during which time the 1.4-dichloro- 2.3-dimethylanthraquinone precipitated from the hot reaction mixture. Upon cooling the mixture to 10 C. there were obtained 41.5 parts of pure 1.4-dichloro-2.3-dimethylanthraquinone melting at 231 to 234 C.
Example II 12 parts of the 1.4-dichloro-2.3-dimethylanthraquinone obtained as in Example I and 75 parts of 20% nitric acid are heated to 200 C. in a pressure vessel for six hours. The yellow crystalline solid obtained was dissolved in dilute sodium hydroxide maintained at 60 C., the solution filtered andthe product recovered by acidification with hydrochloric acid, followed by filtration. There were obtained 9 parts of 1.4- dichlorc-2.3-dicarboxyanthraquinone melting at about 320 C.
Various modifications of the invention will be apparent to persons skilled in the art and we, accordingly, do not intend to be limited in the 3 patent granted except as necessitated by the prior REFERENCES CITED art m appended clalms- The following references are of record in the We 0 file of this patent: 1. Compounds of the followlng formula:
0 X 5 UNITED STATES PATENTS II Number Name Date COOH 1,895,100 Kranzlein et a1 Jan. 24, 1933 1,957,084 Stein May 1, 1934 CO OH 1,966,126 Kranzlein et a1 July 10, 1934 9 1 10 OTHER REFERENCES in which both Xs are the same and are selected i ;g fiz figg Chem GeS"" from the class consisting of chlorine and bromine. schon gf Ber deut'sch Chem Ges V01 2. 1.4-d1chl0ro-2.3-d1carboxyanthraqu1none. 16 67 (1934) pages 1746 1749 FRITZ MAX Fieser et al., "J. Am. Chem. 300., vol. 64 (1942) DAVID I. RANDALL. pages
Claims (1)
1. COMPOUNDS OF THE FOLLOWING FORMULA:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US739250A US2533193A (en) | 1947-04-03 | 1947-04-03 | 2, 3-derivatives of 1, 4-dihaloanthraquinones |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US739250A US2533193A (en) | 1947-04-03 | 1947-04-03 | 2, 3-derivatives of 1, 4-dihaloanthraquinones |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2533193A true US2533193A (en) | 1950-12-05 |
Family
ID=24971462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US739250A Expired - Lifetime US2533193A (en) | 1947-04-03 | 1947-04-03 | 2, 3-derivatives of 1, 4-dihaloanthraquinones |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2533193A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1895100A (en) * | 1927-09-09 | 1933-01-24 | Gen Aniline Works Inc | Ortho-halogenanthraquinonecarboxylic acid and process of preparing it |
| US1957084A (en) * | 1931-08-28 | 1934-05-01 | Gen Aniline Works Inc | Anthraquinone derivative |
| US1966126A (en) * | 1931-11-13 | 1934-07-10 | Gen Aniline Works Inc | Halogen-benzophenone-dicarboxylic acids and halogen-anthraquinone-carboxylic acids and a process of preparing them |
-
1947
- 1947-04-03 US US739250A patent/US2533193A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1895100A (en) * | 1927-09-09 | 1933-01-24 | Gen Aniline Works Inc | Ortho-halogenanthraquinonecarboxylic acid and process of preparing it |
| US1957084A (en) * | 1931-08-28 | 1934-05-01 | Gen Aniline Works Inc | Anthraquinone derivative |
| US1966126A (en) * | 1931-11-13 | 1934-07-10 | Gen Aniline Works Inc | Halogen-benzophenone-dicarboxylic acids and halogen-anthraquinone-carboxylic acids and a process of preparing them |
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